7217-71-2Relevant articles and documents
Size-Exclusion Borane-Catalyzed Domino 1,3-Allylic/Reductive Ireland–Claisen Rearrangements: Impact of the Electronic and Structural Parameters on the 1,3-Allylic Shift Aptitude
Fegyverneki, Dániel,Kolozsvári, Natália,Molnár, Dániel,Egyed, Orsolya,Holczbauer, Tamás,Soós, Tibor
supporting information, p. 2179 - 2183 (2019/01/04)
The reductive Ireland–Claisen rearrangement through borane-mediated hydrosilylation is reported. The method employs a borane catalyst with a special structural design and affords access to synthetically relevant products with high diastereoselectivity. Depending on electronic and structural parameters, the reaction can be coupled with a 1,3-allylic shift, thus the valence isomer of the Ireland–Claisen product is formed.
Base-Free Dynamic Kinetic Resolution of Secondary Alcohols with a Ruthenium-Lipase Couple
Yun, Inyeol,Park, Jin Yong,Park, Jaiwook,Kim, Mahn-Joo
, p. 16293 - 16298 (2019/12/27)
We report the dynamic kinetic resolution (DKR) of various secondary alcohols by the combination of a ruthenium catalyst and an anionic surfactant-activated lipoprotein lipase. The DKR reactions performed under totally base-free conditions at room temperature provided the products of excellent enantiopurities (91-99% ee or greater) in high yields (92-99%). More importantly, the DKR of α-arylallyl alcohols was achieved for the first time with high yields (87-91%).
Pseudomonas sp. Lipase Immobilized on Magnetic Porous Polymer Microspheres as an Effective and Recyclable Biocatalyst for Resolution of Allylic Alcohols
Gu, Yaohua,Xue, Ping
, p. 696 - 705 (2018/06/27)
Magnetic porous polymeric microspheres containing epoxy groups were prepared by suspension polymerization (denoted as magnetic Fe3O4@GEM microspheres). Fe3O4@GEM with a specific surface area of 30.41 m2/g, average pore diameter of 17.13 nm, and pore volume of 0.13 cm3/g exhibited superparamagnetic behavior with the saturation magnetization of 7.1 emu/g. The content of epoxy groups on Fe3O4@GEM was 0.22 mmol/g. Pseudomonas sp. lipase (PSL) was covalently immobilized onto the Fe3O4@GEM microspheres through the reaction between the amino groups of the enzyme and the epoxy groups on the microspheres. PSL/Fe3O4@GEM exhibited enhanced enantioselectivity for the resolution of allylic alcohol to the corresponding optically active (S)-allylic alcohol and (R)-allylic alcohol acetate compared to free PSL. The enantiomeric excess of (S)-l-pheny-2-propen-1-ol for the former (98.1%) was 81.7 times that of the latter (1.2%) when the immobilized PSL was used for transesterification resolution of (R,S)-l-pheny-2-propen-1-ol. Furthermore, the ees and eep values were still retained at 95.2% and 95.4% after PSL/Fe3O4@GEM was recycled 10 times, indicating that PSL/Fe3O4@GEM had very good reusability. In addition, the transesterification resolution of (R,S)-1-(4-methylphenyl)-2-propen-1-ol and (R,S)-1-(4-bromophenyl)-2-propen-1-ol was catalyzed by PSL/Fe3O4@GEM, affording ideal ees and eep values of 99.3%, 97.4% and 99.6%, 98.2%, respectively. Therefore, PSL/Fe3O4@GEM demonstrated its potential as a highly efficient enzymatic reactor and Fe3O4@GEM would be very promising carriers for immobilizing enzymes in industrial application.
A Re2O7catalyzed cycloetherification of monoallylic diols
Wan, Xiaolong,Hu, Jiadong,Xu, Dongyang,Shang, Yang,Zhen, Yanxia,Hu, Chenchen,Xiao, Fan,He, Yu-Peng,Lai, Yisheng,Xie, Weiqing
supporting information, p. 1090 - 1093 (2017/03/02)
A Re2O7catalyzed cycloetherification of monoallylic diols is described. The reaction features short reaction time, mild reaction conditions and exclusive E selectivity. A wide range of monoallylic alcohols with alkyl or aryl substituents on olefin smoothly undergo ring closure to deliver corresponding oxa-heterocycles. The reaction is also operationally simple and not sensitive to air and moisture.
Electrochemical properties and reactions of organoboronic acid esters containing unsaturated bonds at their α-position
Ohtsuka, Kazuhiro,Inagi, Shinsuke,Fuchigami, Toshio
, p. G23 - G28 (2017/12/26)
Electrochemical analyses of 2-(cynnamyl)boronic acid pinacol ester and (3-phenyl-2-propynyl)boronic acid pinacol ester, and their trimethylsilyl analogues as well as their parent compounds were comparatively studied by cyclic voltammetry measurements. We
Kinetic Resolution of Racemic and Branched Monosubstituted Allylic Acetates by a Ruthenium-Catalyzed Regioselective Allylic Etherification
Shinozawa, Toru,Terasaki, Shou,Mizuno, Shota,Kawatsura, Motoi
, p. 5766 - 5774 (2016/07/14)
We demonstrated the kinetic resolution of racemic and branched monosubstituted allylic acetates by a ruthenium-catalyzed regioselective allylic etherification. The reaction was effectively catalyzed by the chiral ruthenium catalyst, which was generated by [RuCl2(p-cymene)]2 and (S,S)-iPr-pybox and a catalytic amount of TFA, and both the allylic etherification product and recovered allylic acetate were obtained as an enantiomerically enriched form with up to a 103 s value.
Flow chemistry as a discovery tool to access sp2-sp3 cross-coupling reactions via diazo compounds
Tran, Duc N.,Battilocchio, Claudio,Lou, Shing-Bong,Hawkins, Joel M.,Ley, Steven V.
, p. 1120 - 1125 (2015/03/04)
The work takes advantage of an important feature of flow chemistry, whereby the generation of a transient species (or reactive intermediate) can be followed by a transfer step into another chemical environment, before the intermediate is reacted with a coupling partner. This concept is successfully applied to achieve a room temperature sp2-sp3 cross coupling of boronic acids with diazo compounds, these latter species being generated from hydrazones under flow conditions using MnO2 as the oxidant.
Organoselenium-catalyzed, hydroxy-controlled regio- and stereoselective amination of terminal alkenes: Efficient synthesis of 3-amino allylic alcohols
Deng, Zhimin,Wei, Jialiang,Liao, Lihao,Huang, Haiyan,Zhao, Xiaodan
supporting information, p. 1834 - 1837 (2015/04/27)
An efficient route to prepare 3-amino allylic alcohols in excellent regio- and stereoselectivity in the presence of bases by orangoselenium catalysis has been developed. In the absence of bases α,β-unsaturated aldehydes were formed in up to 97% yield. Control experiments reveal that the hydroxy group is crucial for the direct amination.
Titanocene(III) chloride mediated radical-induced opening of monosubstituted epoxy acetates for the synthesis of primary allylic alcohols
Chakraborty,Mandal,Roy
, p. 893 - 901 (2015/08/18)
A simple and efficient method for the synthesis of primary allylic alcohols from monosubstituted epoxy acetates has been developed using titanocene(III) chloride mediated epoxide ring opening via acetate elimination.
Homogeneous Pd-catalyzed transformation of terminal alkenes into primary allylic alcohols and derivatives
Tomita, Ren,Mantani, Kohei,Hamasaki, Akiyuki,Ishida, Tamao,Tokunaga, Makoto
supporting information, p. 9914 - 9917 (2014/08/18)
Synthesis of primary alcohols from terminal alkenes is an important process in both bulk and fine chemical syntheses. Herein, a homogeneous Pd-complex-catalyzed transformation of terminal alkenes into primary allylic alcohols, by using 5 mol % [Pd(PPh3)4] as a catalyst, and H2O, CO2, and quinone derivatives as reagents, is reported. When alcohols were used instead of H2O, allylic ethers were obtained. A proposed mechanism includes the addition of oxygen nucleophiles at the less-hindered terminal position of π-allyl Pd intermediates.
